CN108057423A - A kind of preparation method of the chitosan magnetic composite material with characterization of adsorption - Google Patents
A kind of preparation method of the chitosan magnetic composite material with characterization of adsorption Download PDFInfo
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- CN108057423A CN108057423A CN201711263713.7A CN201711263713A CN108057423A CN 108057423 A CN108057423 A CN 108057423A CN 201711263713 A CN201711263713 A CN 201711263713A CN 108057423 A CN108057423 A CN 108057423A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide (Fe3O4)
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
Abstract
The present invention relates to a kind of preparation methods of the chitosan magnetic composite material with characterization of adsorption, the polyimide nano-fiber felt with ultra-hydrophobic high sticking characteristic is prepared first with method of electrostatic spinning, and as the carrier for preparing chitosan magnetic composite material, afterwards by chitosan/Fe3O4Suspension is dropped onto by syringe or sprayer on above-mentioned carrier, and with the quick volatilization of solvent, chitosan shrinks and to Fe3O4Cladding, ultimately forms chitosan magnetic particle.This method is easy to operate, time-consuming short, and avoids the addition of the harmful substances such as glutaraldehyde in conventional method, is a kind of environmental-friendly green preparation process.Prepared chitosan magnetic can be used for the efficient absorption of heavy metal ion, and distinctive magnetism can make the material realize quick separating with immunoabsorbent substrate, and can be recycled for multiple times.
Description
Technical field
The invention belongs to environmentally conscious materials technical fields, are related to a kind of preparation of the chitosan magnetic composite material with characterization of adsorption
Method.
Background technology
With the fast development of social economy and industrial technology, the heavy metal pollution of water body is on the rise.Wherein, the copper in water body
The harm of ion pair organism and the mankind are the most notable.In aquatic ecosystem, when the in vivo copper ion of biology is enriched to one
After determining degree, physiology can be caused to be damaged, arrest of development or even death.And after the copper ion of human body excess intake, liver can be caused
Etc. multiple organ failures, and then seriously endanger human body health.Therefore, exploitation can efficiently remove the technology tool of copper ion in water removal
It is of great significance.
Chitosan, can be with transition containing substantial amounts of amino and hydroxyl on molecular backbone as a kind of natural linear polymeric
Metal ion generates significant chelation, therefore can be as the copper ion in a kind of efficient sorbing material processing waste water.This
Outside, in order to avoid the loss and secondary pollution of adsorbent, usually by chitosan and magnetic Fe3O4Particles dispersed, in order to adsorb
High magnetic separation can be carried out after finishing.This method separative efficiency is high, and convenient for recycling, and automation easy to implement is grasped
Make so that chitosan magnetic adsorbent receives significant attention in actual application.
At present, preparing the method for chitosan magnetic mainly includes inverse suspension crosslinking method, coprecipitation, emulsion-crosslinking method etc..Li
Fe has successfully been prepared Deng using inverse suspension cross-linking method3O4/ Chitosan Composites, wherein chitosan are with covalently bound shape
Formula is coated on Fe3O4Surface forms the homogeneous particle that grain size is 23~25nm.The saturation magnetization of the material is up to 21emu/
G has good Magnetic Isolation effect (G.Y.Li et al., J.Alloy.Compd., 2008,466,451-456).Chen
Deng first dissolving the chitosan in acetic acid solution, afterwards by FeSO4And FeCl3According to 1:2 mass ratio is dissolved in above-mentioned solution
In, NaOH aqueous solutions are added dropwise into mixed liquor again afterwards.FeSO in alkaline conditions4And FeCl3Fe can be generated3O4Particle, same to shell
Glycan forms blending precipitation together, and then obtains composite magnetic chitosan microballoon spheres.The chitosan magnetic obtained using the method is received
Rice complex microsphere the adsorbance of Cu in waste water (II) is up to 35.5mg/g (Y.W.Chen et al., Chem.Eng.J.,
2011,168,286-292).Ma etc. using emulsion-crosslinking method using chitosan as monomer, glutaraldehyde as cross linker, atoleine
For dispersant, Span80 is in the reaction system of emulsifier, is prepared for chitosan magnetic micro-sphere.Obtained magnetic composite microsphere
Uniform particle sizes, good dispersion, similarly for heavy metal ion and dyestuff have good adsorption effect (N.Ma et al.,
Chemical World,2012,12,728-732)。
However, above method there are problems that, such as chitosan magnetic intensity prepared by coprecipitation is relatively low, and shell is easy
Impurity is mixed into, is not suitable for actual production；Inverse suspension cross-linking method and emulsion-crosslinking method are larger with toxicity in preparation process
Glutaraldehyde as cross linker easily pollutes the environment.Therefore, a kind of efficient and environmental-friendly chitosan magnetic for preparing is researched and developed to receive
The method of nano composite material has important Significance for Environment.
The content of the invention
Technical problems to be solved
In order to avoid the shortcomings of the prior art, the present invention proposes a kind of chitosan magnetic composite material with characterization of adsorption
Preparation method.
Technical solution
A kind of preparation method of the chitosan magnetic composite material with characterization of adsorption, it is characterised in that step is as follows：
Step 1 prepares the polyimides PI nanofiber mats with ultra-hydrophobic high sticking characteristic using method of electrostatic spinning：
By polyimides and polyvinylpyrrolidone co-dissolve in solvent A, solution is extracted using syringe, is placed it in quiet
On electric spinning device；Syringe needle is connected with anode, setting spinning voltage is 10~25kV, receives distance as 10~30cm,
Roller rotating speed is 20~40m/min, and the fltting speed of syringe is 0.3~2ml/h；
Fibrofelt is removed after spinning, and is washed 3-5 times successively with deionized water and ethyl alcohol, removes polyvinylpyrrolidone,
Obtain porous PI fibrofelts；
It will tile after ethyl alcohol impregnating porous PI fibrofelts will be used onto stainless steel substrate, is placed in 100 DEG C of vacuum drying chambers and handles
12h is sealed after being cooled to room temperature, and obtains the polyimides PI nanofiber mats with ultra-hydrophobic high sticking characteristic, as
Prepare the carrier of porous magnetic chitosan sorbing material；
The mass ratio of the Ju Xian Ya An ︰ Ju Yi Xi Bi Ka Wan Tong ︰ solvent As is 3g ︰ 0.5~1.5g ︰ 7g；
Step 2：Suspension E is dropped onto on polyimides PI nanofiber mats, is taken out after being heated to 60~140 DEG C, is removed fine
The chitosan magnetic particle on felt is tieed up, the chitosan magnetic particle stripped down is successively with n,N-Dimethylformamide, distilled water,
Ethyl alcohol cleaning is multiple, and magnetic hysteresis separation is carried out after washing, is then dried in vacuo 6~12h at 60~100 DEG C, obtains black magnetic shell
Polysaccharide composite material；
The suspension E：Chitosan and acetic acid water are mixed to form aqueous solution B, and the mass fraction of acetic acid is 1~3%；It will
Fe3O4Microballoon disperses to obtain solution C in aqueous solution, and Fe in solution C3O4Mass fraction be 10~20%；By solution B with
Solution C mixes, and adds alkali metal sulfates and obtains suspension E；Fe in the suspension E3O4︰ Ke Ju Tang ︰ alkali metal sulfates
Mass ratio be 1 ︰, 5~10 ︰ 6~15.
The polyimides is prepared by two-step method：Equipped with the straight of stirring, nitrogen conduit, thermometer and Dean-Stark devices
3~5g 4, the double phthalic anhydrides of 4- (hexafluoro isopropyl) and 27.2~45.4g N, N- dimethyl are sequentially added in four-hole bottle
Acetamide then adds in 0.17~0.28g 1,3- diaminopropyls tetramethyl disiloxane and 1.58~2.64g1,3.4- tri-
Two ether diamine of phenyl is eventually adding 0.05~0.09g, 2,4,6- Triaminopyrimidines, reaction 30 is stirred at room temperature under nitrogen atmosphere
~36h；Then the meta-xylene of 15~25ml is added in into the system, 150~170 DEG C of 10~15h of reaction is warming up to, is gathered
Imide solution；It pours this solution into 500ml ethyl alcohol, is filtered after precipitating, filter cake is washed 3-5 times with ethyl alcohol, and at 150 DEG C
Dry 12h obtains polyimide powder in vacuum drying oven.
The Fe3O4Grain size be 200~600nm.
The Fe3O4Method for preparing microsphere：By the FeCl of 5~10mmol3﹒ 6H2The sodium citrate of O and 10~20mmol is dissolved in
In 80ml water, 1~3g urea is added in after magnetic agitation, 0.6~1.2g polyacrylamides is added in after reacting 10min, reacts 2~5h
Solution is transferred in the stainless steel polytetrafluoro autoclave of 100ml afterwards and 6~12h is reacted at 200 DEG C；Reaction terminates
Afterwards, cooled to room temperature, product through ethyl alcohol and distill water washing three times successively, 12~20h are dried in vacuo at 100 DEG C, is obtained
To nanoscale Fe3O4Microballoon.
The solvent A is any one or its group in n,N-Dimethylformamide, n,N-dimethylacetamide, tetrahydrofuran
It closes.
The alkali metal sulfates for sodium sulphate, magnesium sulfate, potassium sulfate any one or its combination.
The step 2 drops onto suspension E on polyimides PI nanofiber mats through syringe or sprayer.
The step 2 is successively with n,N-Dimethylformamide, distilled water, ethyl alcohol cleaning 2~3 times.
Deacetylation >=95% of chitosan, the mass fraction of acetic acid is 1~3% in solution A, and the mass fraction of chitosan is
3.5~5%.
Advantageous effect
The preparation method of a kind of chitosan magnetic composite material with characterization of adsorption proposed by the present invention, first with Static Spinning
Silk method constructs the porous PI fibrofelts with ultra-hydrophobic high sticking characteristic, as the basis material for preparing chitosan magnetic.
Again by chitosan magnetic drips to fibrofelt surface, with the quick volatilization of solvent, chitosan shrinks and to Fe3O4Cladding,
And then form chitosan magnetic particle.This method obviates water phase or lotion phase system used by conventional method completely, without
The larger glutaraldehyde of toxicity is added in be crosslinked, it is efficient and environment friendly and pollution-free.From drips to chitosan magnetic grain forming
It only needs 5~10 minutes, has embodied very high production efficiency, be very beneficial for industrial mass production.In addition, as carrier
PI porous fibre felts repeat utilization, will not cause to waste.
The chitosan magnetic particle prepared using method proposed by the present invention has apparent porous structure, and large specific surface area is right
Cu (II) has good adsorption effect, and maximal absorptive capacity is up to 95.8mg/g.It can be achieved after absorption using rapid magnetic separation
The high efficiente callback of sorbing material recycles, and after recycling 5 times, the adsorption efficiency of the chitosan magnetic particle remains to keep
65%, embody prominent economic benefit and environmental benefit.
Description of the drawings
Fig. 1：The scanning electron microscopic picture of porous PI fibrofelts in embodiment 1；
Fig. 2：The Contact-angle measurement picture of porous PI fibrofelts in embodiment 1
Fig. 3：Prepared Fe in embodiment 1-83O4Scanning electron microscopic picture
Fig. 4：The scanning electron microscopic picture of chitosan magnetic particle in embodiment 1；
Fig. 5：Fe in embodiment 1-23O4, chitosan magnetic material hysteresis loop；
Fig. 6：To the adsorbance of Cu (II) when chitosan magnetic cycles samples use 1-5 times in embodiment 6；
Fig. 7：Chitosan magnetic sample is to the curve of adsorption kinetics of Cu (II) in embodiment 4-6.
Specific embodiment
In conjunction with embodiment, attached drawing, the invention will be further described：
Embodiment 1
1)：3g polyimides and 0.5g polyvinylpyrrolidones are dissolved in jointly in 7g n,N-Dimethylformamide, and ultrasonic vibration makes
It is completely dissolved.Solution is extracted using 10ml syringes, places it on electrostatic spinning apparatus, anode is connected to syringe needle
Head starts spinning.Spinning voltage is 10kV, receives distance as 10cm, and roller rotating speed is 25m/min.Fibre is removed after spinning
Felt is tieed up, removal polyvinylpyrrolidone is cleaned repeatedly using pure water and ethyl alcohol, obtains porous PI fibrofelts, used ethyl alcohol afterwards
Infiltration is tiled onto stainless steel substrate, is placed on 12h in 100 DEG C of vacuum drying chambers, is sealed after taking-up, magnetic as preparing
The matrix of chitosan sorbing material.The polyimides that this step is used is synthesized by traditional two-step method, is as follows：
Sequentially adding 4.44g4,4- in straight four-hole bottle equipped with stirring, nitrogen conduit, thermometer and Dean-Stark devices, (hexafluoro is different
Propyl) double phthalic anhydrides and 40.28gN, N- dimethyl acetamide, then add in 0.25g1,3- diaminopropyl tetramethyls
Two ether diamine of disiloxane and 2.34g1,3.4- triphenyl, adds 0.08g2,4,6- Triaminopyrimidines, under nitrogen atmosphere
32h is reacted at room temperature, afterwards to the meta-xylene that 20ml is added in reaction solution, 160 DEG C of reaction 15h is warming up to, obtains polyimides
Solution.It pours this solution into 500ml ethyl alcohol, is filtered after precipitating, after filter cake is washed three times with ethyl alcohol, in vacuum drying oven
150 DEG C of dry 12h, obtain polyimide powder.
2)：Chitosan is dissolved in acetic acid aqueous solution, ultrasonic vibration makes it fully dissolve, and obtains solution A.The wherein quality of acetic acid
Fraction is 1%, and the mass fraction of chitosan is 3.5%.
3)：Nanoscale Fe is prepared using hydro-thermal method3O4Microballoon, and its is fully dispersed in aqueous solution, obtain solution B.Wherein
Fe3O4Mass fraction be 10%.Nanoscale Fe3O4Method for preparing microsphere is as follows：By the FeCl of 5mmol3﹒ 6H2O's and 10mmol
Sodium citrate is dissolved in 80ml water, and 1g urea is added in after magnetic agitation 30min, 0.6g poly- third is added in after magnetic agitation 10min
Solution is transferred in the stainless steel polytetrafluoro autoclave of 100ml after magnetic agitation 2h, is reacted at 200 DEG C by acrylamide
12h.After reaction, product by ethyl alcohol and is distilled water washing three times by cooled to room temperature successively, true at 100 DEG C
The dry 12h of sky, obtains nanoscale Fe3O4Microballoon.
4)：Solution A and solution B are mixed according to a certain percentage, uniform solution is obtained by mechanical agitation, in whipping process to
The sodium sulphate of 0.5g is added in solution, chitosan is precipitated, obtains suspension C.
5)：On the porous PI nanofiber mats that suspension C is dropped onto to step 1) preparation by sprayer, fibrofelt is turned
It moves in 60 DEG C of baking ovens to heat and take out after ten minutes, remove the chitosan magnetic particle on fibrofelt, magnetic hysteresis point is carried out after washing
From, it is dry, obtain black magnetic chitosan product.
Embodiment 2
1)：3g polyimides and 1g polyvinylpyrrolidones are dissolved in jointly in 7g n,N-dimethylacetamide, and ultrasonic vibration makes it
It is completely dissolved.Solution is extracted using 10ml syringes, places it on electrostatic spinning apparatus, anode is connected to syringe needle,
Start spinning.Spinning voltage is 10kV, receives distance as 15cm, and roller rotating speed is 30m/min.Fiber is removed after spinning
Felt cleans removal polyvinylpyrrolidone repeatedly using pure water and ethyl alcohol, obtains porous PI fibrofelts, afterwards soaks it with ethyl alcohol
Profit tiling is placed on 12h in 100 DEG C of vacuum drying chambers, is sealed after taking-up on stainless steel substrate, as preparing magnetic crust
The matrix of glycan sorbing material.The polyimides that this step is used is synthesized by traditional two-step method, the same embodiment of specific steps
1。
2)：Chitosan is dissolved in acetic acid aqueous solution, ultrasonic vibration makes it fully dissolve, and obtains solution A.The wherein quality of acetic acid
Fraction is 1%, and the mass fraction of chitosan is 3.5%.
3)：Nanoscale Fe is prepared using hydro-thermal method3O4Microballoon, and its is fully dispersed in aqueous solution, obtain solution B.Wherein
Fe3O4Mass fraction be 20%.Nanoscale Fe3O4Method for preparing microsphere is the same as embodiment 1.
4)：Solution A and solution B are mixed according to a certain percentage, uniform solution is obtained by mechanical agitation, in whipping process to
The potassium sulfate of 0.5g is added in solution, chitosan is precipitated, obtains suspension C.
5)：On the porous PI nanofiber mats that suspension C is dropped onto to step 1) preparation by sprayer, fibrofelt is transferred to
It is taken out after being heated 8 minutes in 80 DEG C of baking ovens, removes the chitosan magnetic particle on fibrofelt, magnetic hysteresis separation is carried out after washing, done
It is dry, obtain black magnetic chitosan product.
Embodiment 3
1)：3g polyimides and 1.5g polyvinylpyrrolidones are dissolved in jointly in 7g tetrahydrofurans, and ultrasonic vibration makes it completely molten
Solution.Solution is extracted using 10ml syringes, places it on electrostatic spinning apparatus, anode is connected to syringe needle, start to spin
Silk.Spinning voltage is 15kV, receives distance as 20cm, and roller rotating speed is 40m/min.Fibrofelt is removed after spinning, is utilized
Pure water and ethyl alcohol clean removal polyvinylpyrrolidone repeatedly, obtain porous PI fibrofelts, it are infiltrated with ethyl alcohol tile afterwards
Onto stainless steel substrate, 12h in 100 DEG C of vacuum drying chambers is placed on, is sealed after taking-up, inhaled as chitosan magnetic is prepared
The matrix of enclosure material.The polyimides that this step is used is synthesized by traditional two-step method, and specific steps are the same as embodiment 1.
2)：Chitosan is dissolved in acetic acid aqueous solution, ultrasonic vibration makes it fully dissolve, and obtains solution A.The wherein quality of acetic acid
Fraction is 2%, and the mass fraction of chitosan is 3.5%.
3)：Nanoscale Fe is prepared using hydro-thermal method3O4Microballoon, and its is fully dispersed in aqueous solution, obtain solution B.Its
Middle Fe3O4Mass fraction be 10%.Nanoscale Fe3O4Method for preparing microsphere is the same as embodiment 1.
4)：Solution A and solution B are mixed according to a certain percentage, uniform solution is obtained by mechanical agitation, in whipping process to
The sodium sulphate of 0.5g is added in solution, chitosan is precipitated, obtains suspension C.
5)：On the porous PI nanofiber mats that suspension C is dropped onto to step 1) preparation by sprayer, fibrofelt is transferred to
It is taken out after being heated 6 minutes in 100 DEG C of baking ovens, removes the chitosan magnetic particle on fibrofelt, magnetic hysteresis separation is carried out after washing, done
It is dry, obtain black magnetic chitosan product.
Embodiment 4
1)：3g polyimides and 1g polyvinylpyrrolidones are dissolved in jointly in 7g n,N-Dimethylformamide, and ultrasonic vibration makes it
It is completely dissolved.Solution is extracted using 10ml syringes, places it on electrostatic spinning apparatus, anode is connected to syringe needle,
Start spinning.Spinning voltage is 20kV, receives distance as 15cm, and roller rotating speed is 40m/min.Fiber is removed after spinning
Felt cleans removal polyvinylpyrrolidone repeatedly using pure water and ethyl alcohol, obtains porous PI fibrofelts, afterwards soaks it with ethyl alcohol
Profit tiling is placed on 12h in 100 DEG C of vacuum drying chambers, is sealed after taking-up on stainless steel substrate, as preparing magnetic crust
The matrix of glycan sorbing material.The polyimides that this step is used is synthesized by traditional two-step method, the same embodiment of specific steps
1。
2)：Chitosan is dissolved in acetic acid aqueous solution, ultrasonic vibration makes it fully dissolve, and obtains solution A.The wherein quality of acetic acid
Fraction is 2%, and the mass fraction of chitosan is 5%.
3)：Nanoscale Fe is prepared using hydro-thermal method3O4Microballoon, and its is fully dispersed in aqueous solution, obtain solution B.Wherein
Fe3O4Mass fraction be 20%.Nanoscale Fe3O4Method for preparing microsphere is the same as embodiment 1.
4)：Solution A and solution B are mixed according to a certain percentage, uniform solution is obtained by mechanical agitation, in whipping process to
The sodium sulphate of 0.5g is added in solution, chitosan is precipitated, obtains suspension C.
5)：On the porous PI nanofiber mats that suspension C is dropped onto to step 1) preparation by sprayer, fibrofelt is transferred to
It heats in 140 DEG C of baking ovens and takes out after five minutes, remove the chitosan magnetic particle on fibrofelt, magnetic hysteresis separation is carried out after washing, do
It is dry, obtain black magnetic chitosan product.
Embodiment 5
1)：3g polyimides and 1g polyvinylpyrrolidones are dissolved in jointly in 7g n,N-Dimethylformamide, and ultrasonic vibration makes it
It is completely dissolved.Solution is extracted using 10ml syringes, places it on electrostatic spinning apparatus, anode is connected to syringe needle,
Start spinning.Spinning voltage is 20kV, receives distance as 15cm, and roller rotating speed is 40m/min.Fiber is removed after spinning
Felt cleans removal polyvinylpyrrolidone repeatedly using pure water and ethyl alcohol, obtains porous PI fibrofelts, afterwards soaks it with ethyl alcohol
Profit tiling is placed on 12h in 100 DEG C of vacuum drying chambers, is sealed after taking-up on stainless steel substrate, as preparing magnetic crust
The matrix of glycan sorbing material.The polyimides that this step is used is synthesized by traditional two-step method, the same embodiment of specific steps
1。
2)：Chitosan is dissolved in acetic acid aqueous solution, ultrasonic vibration makes it fully dissolve, and obtains solution A.The wherein quality of acetic acid
Fraction is 2%, and the mass fraction of chitosan is 5%.
3)：Nanoscale Fe is prepared using hydro-thermal method3O4Microballoon, and its is fully dispersed in aqueous solution, obtain solution B.Wherein
Fe3O4Mass fraction be 10%.Nanoscale Fe3O4Method for preparing microsphere is the same as embodiment 1.
4)：Solution A and solution B are mixed according to a certain percentage, uniform solution is obtained by mechanical agitation, in whipping process
The middle sodium sulphate that 0.3g is added in into solution, is precipitated chitosan, obtains suspension C.
5)：On the porous PI nanofiber mats that suspension C is dropped onto to step 1) preparation by sprayer, fibrofelt is transferred to
It heats in 140 DEG C of baking ovens and takes out after five minutes, remove the chitosan magnetic particle on fibrofelt, magnetic hysteresis separation is carried out after washing, do
It is dry, obtain black magnetic chitosan product.
Embodiment 6
1)：3g polyimides and 1g polyvinylpyrrolidones are dissolved in jointly in 7g n,N-dimethylacetamide, and ultrasonic vibration makes it
It is completely dissolved.Solution is extracted using 10ml syringes, places it on electrostatic spinning apparatus, anode is connected to syringe needle,
Start spinning.Spinning voltage is 20kV, receives distance as 15cm, and roller rotating speed is 40m/min.Fiber is removed after spinning
Felt cleans removal polyvinylpyrrolidone repeatedly using pure water and ethyl alcohol, obtains porous PI fibrofelts, afterwards soaks it with ethyl alcohol
Profit tiling is placed on 12h in 100 DEG C of vacuum drying chambers, is sealed after taking-up on stainless steel substrate, as preparing magnetic crust
The matrix of glycan sorbing material.The polyimides that this step is used is synthesized by traditional two-step method, the same embodiment of specific steps
1。
2)：Chitosan is dissolved in acetic acid aqueous solution, ultrasonic vibration makes it fully dissolve, and obtains solution A.The wherein quality of acetic acid
Fraction is 2%, and the mass fraction of chitosan is 5%.
3)：Nanoscale Fe is prepared using hydro-thermal method3O4Microballoon, and its is fully dispersed in aqueous solution, obtain solution B.Wherein
Fe3O4Mass fraction be 10%.Nanoscale Fe3O4Method for preparing microsphere is the same as embodiment 1.
4)：Solution A and solution B are mixed according to a certain percentage, uniform solution is obtained by mechanical agitation, in whipping process to
The sodium sulphate of 0.7g is added in solution, chitosan is precipitated, obtains suspension C.
5)：On the porous PI nanofiber mats that suspension C is dropped onto to step 1) preparation by sprayer, fibrofelt is transferred to
It heats in 140 DEG C of baking ovens and takes out after five minutes, remove the chitosan magnetic particle on fibrofelt, magnetic hysteresis separation is carried out after washing, do
It is dry, obtain black magnetic chitosan product.
Embodiment 7
1)：3g polyimides and 1g polyvinylpyrrolidones are dissolved in jointly in 7g tetrahydrofurans, and ultrasonic vibration is completely dissolved it.
Solution is extracted using 10ml syringes, is placed it on electrostatic spinning apparatus, anode is connected to syringe needle, starts spinning.
Spinning voltage is 20kV, receives distance as 15cm, and roller rotating speed is 40m/min.Fibrofelt is removed after spinning, utilizes pure water
It cleans removal polyvinylpyrrolidone repeatedly with ethyl alcohol, obtains porous PI fibrofelts, afterwards arrive it not with ethyl alcohol infiltration tiling
It becomes rusty on steel substrate, is placed on 12h in 100 DEG C of vacuum drying chambers, is sealed after taking-up, as preparing chitosan magnetic adsorption material
The matrix of material.The polyimides that this step is used is synthesized by traditional two-step method, and specific steps are the same as embodiment 1.
2)：Chitosan is dissolved in acetic acid aqueous solution, ultrasonic vibration makes it fully dissolve, and obtains solution A.The wherein quality of acetic acid
Fraction is 2%, and the mass fraction of chitosan is 5%.
3)：Nanoscale Fe is prepared using hydro-thermal method3O4Microballoon, and its is fully dispersed in aqueous solution, obtain solution B.Wherein
Fe3O4Mass fraction be 20%.Nanoscale Fe3O4Method for preparing microsphere is the same as embodiment 1.
4)：Solution A and solution B are mixed according to a certain percentage, uniform solution is obtained by mechanical agitation, in whipping process to
The magnesium sulfate of 0.7g is added in solution, chitosan is precipitated, obtains suspension C.
5)：On the porous PI nanofiber mats that suspension C is dropped onto to step 1) preparation by syringe, fibrofelt is transferred to
It is taken out after being heated 8 minutes in 100 DEG C of baking ovens, removes the chitosan magnetic particle on fibrofelt, magnetic hysteresis separation is carried out after washing, done
It is dry, obtain black magnetic chitosan product.
Embodiment 8
1)：3g polyimides and 1g polyvinylpyrrolidones are dissolved in jointly in 7g n,N-Dimethylformamide, and ultrasonic vibration makes it
It is completely dissolved.Solution is extracted using 10ml syringes, places it on electrostatic spinning apparatus, anode is connected to syringe needle,
Start spinning.Spinning voltage is 20kV, receives distance as 15cm, and roller rotating speed is 40m/min.Fiber is removed after spinning
Felt cleans removal polyvinylpyrrolidone repeatedly using pure water and ethyl alcohol, obtains porous PI fibrofelts, afterwards soaks it with ethyl alcohol
Profit tiling is placed on 12h in 100 DEG C of vacuum drying chambers, is sealed after taking-up on stainless steel substrate, as preparing magnetic crust
The matrix of glycan sorbing material.The polyimides that this step is used is synthesized by traditional two-step method, the same embodiment of specific steps
1。
2)：Chitosan is dissolved in acetic acid aqueous solution, ultrasonic vibration makes it fully dissolve, and obtains solution A.The wherein quality of acetic acid
Fraction is 2%, and the mass fraction of chitosan is 5%.
3)：Nanoscale Fe is prepared using hydro-thermal method3O4Microballoon, and its is fully dispersed in aqueous solution, obtain solution B.Wherein
Fe3O4Mass fraction be 20%.Nanoscale Fe3O4Method for preparing microsphere is the same as embodiment 1.
4)：Solution A and solution B are mixed according to a certain percentage, uniform solution is obtained by mechanical agitation, in whipping process to
The potassium sulfate of 0.7g is added in solution, chitosan is precipitated, obtains suspension C.
5)：On the porous PI nanofiber mats that suspension C is dropped onto to step 1) preparation by syringe, fibrofelt is transferred to
It heats in 60 DEG C of baking ovens and takes out after ten minutes, remove the chitosan magnetic particle on fibrofelt, magnetic hysteresis separation is carried out after washing, do
It is dry, obtain black magnetic chitosan product.
Claims (8)
1. a kind of preparation method of the chitosan magnetic composite material with characterization of adsorption, it is characterised in that step is as follows：
Step 1 prepares the polyimides PI nanofiber mats with ultra-hydrophobic high sticking characteristic using method of electrostatic spinning：
By polyimides and polyvinylpyrrolidone co-dissolve in solvent A, solution is extracted using syringe, is placed it in quiet
On electric spinning device；Syringe needle is connected with anode, setting spinning voltage is 10~25kV, receives distance as 10~30cm,
Roller rotating speed is 20~40m/min, and the fltting speed of syringe is 0.3~2ml/h；
Fibrofelt is removed after spinning, and is washed 3-5 times successively with deionized water and ethyl alcohol, removes polyvinylpyrrolidone,
Obtain porous PI fibrofelts；
It will tile after ethyl alcohol impregnating porous PI fibrofelts will be used onto stainless steel substrate, is placed in 100 DEG C of vacuum drying chambers and handles
12h is sealed after being cooled to room temperature, and obtains the polyimides PI nanofiber mats with ultra-hydrophobic high sticking characteristic, as
Prepare the carrier of porous magnetic chitosan sorbing material；
The mass ratio of the Ju Xian Ya An ︰ Ju Yi Xi Bi Ka Wan Tong ︰ solvent As is 3g ︰ 0.5~1.5g ︰ 7g；
Step 2：Suspension E is dropped onto on polyimides PI nanofiber mats, is taken out after being heated to 60~140 DEG C, is removed fine
The chitosan magnetic particle on felt is tieed up, the chitosan magnetic particle stripped down is successively with n,N-Dimethylformamide, distilled water,
Ethyl alcohol cleaning is multiple, and magnetic hysteresis separation is carried out after washing, is then dried in vacuo 6~12h at 60~100 DEG C, obtains black magnetic shell
Polysaccharide composite material；
The suspension E：Chitosan and acetic acid water are mixed to form aqueous solution B, and the mass fraction of acetic acid is 1~3%；It will
Fe3O4Microballoon disperses to obtain solution C in aqueous solution, and Fe in solution C3O4Mass fraction be 10~20%；By solution B with
Solution C mixes, and adds alkali metal sulfates and obtains suspension E；Fe in the suspension E3O4︰ Ke Ju Tang ︰ alkali metal sulfates
Mass ratio be 1 ︰, 5~10 ︰ 6~15.
2. the preparation method of the chitosan magnetic composite material with characterization of adsorption according to claim 1, it is characterised in that：
The polyimides is prepared by two-step method：In the Zhi Sikou equipped with stirring, nitrogen conduit, thermometer and Dean-Stark devices
3~5g 4, the double phthalic anhydrides of 4- (hexafluoro isopropyl) and 27.2~45.4g N, N- dimethylacetamides are sequentially added in bottle
Amine then adds in 0.17~0.28g 1,3- diaminopropyls tetramethyl disiloxane and 1.58~2.64g 1,3.4- triphenyl
Two ether diamines are eventually adding 0.05~0.09g, 2,4,6- Triaminopyrimidines, be stirred at room temperature under nitrogen atmosphere reaction 30~
36h；Then the meta-xylene of 15~25ml is added in into the system, 150~170 DEG C of 10~15h of reaction is warming up to, obtains polyamides
Imide liquor；It pours this solution into 500ml ethyl alcohol, is filtered after precipitating, filter cake is washed 3-5 times with ethyl alcohol, and it is true at 150 DEG C
Dry 12h obtains polyimide powder in empty baking oven.
3. the preparation method of the chitosan magnetic composite material with characterization of adsorption according to claim 1, it is characterised in that：
The Fe3O4Grain size be 200~600nm.
4. the preparation method of the chitosan magnetic composite material with characterization of adsorption, feature exist according to claim 1 or 3
In：The Fe3O4Method for preparing microsphere：By the FeCl of 5~10mmol3﹒ 6H2The sodium citrate of O and 10~20mmol is dissolved in
In 80ml water, 1~3g urea is added in after magnetic agitation, 0.6~1.2g polyacrylamides is added in after reacting 10min, reacts 2~5h
Solution is transferred in the stainless steel polytetrafluoro autoclave of 100ml afterwards and 6~12h is reacted at 200 DEG C；Reaction terminates
Afterwards, cooled to room temperature, product through ethyl alcohol and distill water washing three times successively, 12~20h are dried in vacuo at 100 DEG C, is obtained
To nanoscale Fe3O4Microballoon.
5. the preparation method of the chitosan magnetic composite material with characterization of adsorption according to claim 1, it is characterised in that：
The solvent A is any one or its combination in n,N-Dimethylformamide, n,N-dimethylacetamide, tetrahydrofuran.
6. the preparation method of the chitosan magnetic composite material with characterization of adsorption according to claim 1, it is characterised in that：
The alkali metal sulfates for sodium sulphate, magnesium sulfate, potassium sulfate any one or its combination.
7. the preparation method of the chitosan magnetic composite material with characterization of adsorption according to claim 1, it is characterised in that：
The step 2 drops onto suspension E on polyimides PI nanofiber mats through syringe or sprayer.
8. the preparation method of the chitosan magnetic composite material with characterization of adsorption according to claim 1, it is characterised in that：
The step 2 is successively with n,N-Dimethylformamide, distilled water, ethyl alcohol cleaning 2~3 times.
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| CN113308753A (en) * | 2021-05-31 | 2021-08-27 | 陕西科技大学 | High-temperature adsorbable porous polyimide nanofiber and preparation method and application thereof |
| CN115337791A (en) * | 2022-09-02 | 2022-11-15 | 万华化学集团股份有限公司 | Hollow fiber porous membrane and preparation method and application thereof |
| CN115888815A (en) * | 2022-10-25 | 2023-04-04 | 湖北工程学院 | Preparation of N-maleylation chitosan copper catalyst and application of N-maleylation chitosan copper catalyst in boron addition reaction |
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| US20130270180A1 (en) * | 2010-10-28 | 2013-10-17 | Novarials Corporation | Ceramic nanowire membranes and methods of making the same |
| CN104342852A (en) * | 2014-10-27 | 2015-02-11 | 东华大学 | Preparation methods of porous carbon nanofiber felt and porous carbon nanofiber electrode |
| CN104437395A (en) * | 2014-11-03 | 2015-03-25 | 中国科学院过程工程研究所 | Acid-resistant magnetic chitosan microspheres as well as preparation method and application thereof |
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| CN104342852A (en) * | 2014-10-27 | 2015-02-11 | 东华大学 | Preparation methods of porous carbon nanofiber felt and porous carbon nanofiber electrode |
| CN104437395A (en) * | 2014-11-03 | 2015-03-25 | 中国科学院过程工程研究所 | Acid-resistant magnetic chitosan microspheres as well as preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113308753A (en) * | 2021-05-31 | 2021-08-27 | 陕西科技大学 | High-temperature adsorbable porous polyimide nanofiber and preparation method and application thereof |
| CN115337791A (en) * | 2022-09-02 | 2022-11-15 | 万华化学集团股份有限公司 | Hollow fiber porous membrane and preparation method and application thereof |
| CN115337791B (en) * | 2022-09-02 | 2024-05-03 | 万华化学集团股份有限公司 | Hollow fiber porous membrane and preparation method and application thereof |
| CN115888815A (en) * | 2022-10-25 | 2023-04-04 | 湖北工程学院 | Preparation of N-maleylation chitosan copper catalyst and application of N-maleylation chitosan copper catalyst in boron addition reaction |
| CN115888815B (en) * | 2022-10-25 | 2024-03-19 | 湖北工程学院 | Preparation of N-maleylation chitosan copper catalyst and application of catalyst in boron addition reaction |
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